Glyoxal/cyclic urea condensates

ABSTRACT

Alkylated glyoxal/cyclic urea condensates are excellent formaldehyde-free crosslinking resins for textile fabrics.

This application is a continuation-in-part of application Ser. No.092,630 (filed Nov. 8, 1979), now abandoned.

This invention relates to novel textile finishing agents. Moreparticularly it relates to novel finishing resins that impart permanentpress characteristics to textile fabrics.

BACKGROUND OF THE INVENTION

The use of thermosetting resins or reactants to impart crease resistanceand dimensional stability of textile materials is well-known in the art.These materials, known as "aminoplast resins", include the products ofthe reaction of formaldehyde with such compounds as urea, thiourea,ethylene urea, dihydroxyethylene urea, melamines, or the like. A seriousdrawback to the use of such materials is that they contain freeformaldehyde. This is present during the preparation and storage of thefinishing agent and its use in treating textiles, on the treated fabric,and on the finished garments. Also, when the fabrics or garments madetherefrom are stored under humid conditions, additional freeformaldehyde is produced.

The presence of even less than one percent of free formaldehyde, basedon the total weight of the product, is undesirable, not only because ofits unpleasant odor, but because it is an allergen and an irritant,causing severe reactions in the operators who manufacture the agent andwho treat and handle the treated fabrics and to persons who handle andwear garments fabricated from the treated fabrics.

These problems associated with the presence of free formaldehyde ontreated fabrics are well-known and considerable efforts have been madeto produce formaldehyde-free textile fabrics. One solution to theproblems has been to employ scavengers for the free formaldehyde. InU.S. Pat. No. 3,590,100 cyclic ethylene urea and propylene urea aredisclosed as scavengers. Removal of the formaldehyde by reaction withphthalimide is disclosed in U.S. Pat. No. 3,723,058. U.S. Pat. No.4,127,382 teaches certain nitrogen-containing heterocyclic compounds asscavengers.

Treating textiles with resin compositions that do not contain or evolveformaldehyde is also known, as in U.S. Pat. No. 3,260,565 which teachesfinishing agents formed by the reaction of alkyl or aryl ureas orthioureas with glyoxal. These agents, however, have the disadvantage ofhaving marginal permanent press properties. Finishing agents formed bythe reaction of ethylene urea with glyoxal are disclosed in Japanesepublication No. 5 3044-567, but they too do not have satisfactoryproperties.

SUMMARY OF THE INVENTION

It has now been found that the alkylated products of the reaction ofglyoxal and cyclic ureas are excellent crosslinking resins for textilefabrics and do not contain formaldehyde.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the present invention, novel alkylated glyoxal/cyclicurea condensates are prepared that are useful for crosslinking textilefabrics

The cyclic ureas which may be used have the following general formulas:##STR1## wherein R₁, R₂, R₃, R₄, R₅, and R₆ may be the same or differentand each may be H, OH, COOH, R, OR, or COOR wherein R is an alkyl or asubstituted alkyl group having 1 to 4 carbon atoms, and X may be C, O,or N; when X is O, R₃ and R₄ are each zero; when X is N, R₃ or R₄ iszero.

Typical examples of such compounds include, but are not limited to,ethylene urea, propylene urea, uron,tetrahydro-5-(2-hydroxyethyl)-1,3,5-triazin-2-one,4,5-dihydroxy-2-imidazolidinone, 4,5-dimethoxy-2-imidazolidinone,4-methyl ethylene urea, 4-ethyl ethylene urea, 4-hydroxyethyl ethyleneurea, 4,5-dimethyl ethylene urea, 4-hydroxy-5-methyl propylene urea,4-methoxy-5-methyl propylene urea, 4-hydroxy-5,5-dimethyl propyleneurea, 4-methoxy-5,5-dimethyl propylene urea, tetrahydro-5-(ethyl)-1,3,5-triazin-2-one, tetrahydro-5-(propyl)-1,3,5-triazin-2-one,tetrahydro-5-(butyl)-1,3,5-triazin-2-one, and the like, and mixtures ofthese.

The alkylated condensates can be prepared by any suitable and convenientprocedure. The cyclic urea and the glyoxal are generally reacted instoichiometric amounts, although a slight excess of either of thereactants may be employed. The general range of glyoxal:cyclic urea isabout 0.8-1.2:1. The reaction may be carried out within the temperaturerange of room temperature up to reflux, but preferably is run at about50° to 60° C. for about two hours. The pH may range from about 2 to 7.0,and preferably it is within the range of about 5.0 to 7.0. The productis a water-soluble oligomer. These glyoxal/cyclic urea condensates arethen partially or wholly alkylated, e.g., by reacting them with analcohol such as methanol, ethanol, n-propanol, a butanol, and the like,and their mixtures. Another method involves reacting glyoxal with analkylated cyclic urea.

The treating agent of this invention is suitable for use with cellulosictextile fabrics, woven or non-woven, including 100% cellulosic fabrics,e.g., cotton, rayon, and linen, as well as blends, e.g.,polyester/cotton or polyester/rayon. Such blends preferably but notnecessarily contain at least 20% of cellulose. Both white and colored(printed, dyed, yarn-dyed, cross-dyed, etc.) fabrics can be effectivelytreated with the resins of this invention. It is applicable also tofabrics containing fibers with free hydroxyl groups.

When applying the resin of this invention to a fabric, there generallywill be present an appropriate catalyst. Typical catalysts include acids(such as hydrochloric, sulfuric, fluoboric, acetic, glycolic, maleic,lactic, citric, tartaric, and oxalic acids); metal salts (such asmagnesium chloride, nitrate, fluoborate, or fluosilicate; zinc chloride,nitrate, fluoborate, or fluosilicate; ammonium chloride; zirconiumoxychloride; sodium or potassium bisulfate); amine hydrochlorides (suchas the hydrochloride of 2-amino-2-methyl-1-propanol); and the like, andmixtures thereof. The amount of catalyst generally is about 0.01 to 10percent, and preferably about 0.05 to 5 percent, based on the weight ofthe padding bath.

The finishing agents may be applied to the textile fabric in any knownand convenient manner, e.g., by dipping or padding, and will generallybe applied from aqueous or alcoholic solution. The solvent may be water;an aliphatic alcohol, e.g., methanol, ethanol, or isopropanol; or amixture of water and an aliphatic alcohol. Other conventional additivessuch as lubricants, softeners, bodying agents, water repellents, flameretardants, soil shedding agents, mildew inhibitors, anti-wet soilingagents, fluorescent brighteners, and the like may be used in thetreating bath in conventional amounts. Such auxiliaries must not,however, interfere with the proper functioning of the finishing resin,must not themselves have a deleterious effect on the fabric, anddesirably are free of formaldehyde.

The amount of treating agent which is applied to the fabric will dependupon the type of fabric and its intended application. In general it isabout 0.5 to 10 percent, and preferably about 2 to 5 percent, based onthe weight of the fabric.

In the process of treating fabrics with the resins of this invention,the fabric is impregnated with an aqueous or alcoholic solution of thefinishing resin, and the impregnated fabric is then dried and cured; thedrying and curing steps may be consecutive or simultaneous.

If desired, the textile fabric may be finished by post-curing (alsoknown as deferred or delayed curing). This consists of impregnating thefabric with a solution of the finishing resin and catalyst; drying theimpregnated material carefully so that the finishing agent does notreact; and then, after a prolonged interval, heating the material to atemperature at which the agent reacts under the influence of thecatalyst.

Although this invention will be described with the use of the alkylatedproduct of the reaction of a cyclic urea and glyoxal as a textilefinishing agent in this application and as an insolubilizer for bindersin paper coatings in copending application Ser. No. 092,631 (filed Nov.8, 1979), it is not intended to be limited thereto. It is also suitablefor use as a dry-strength or a wet-strength resin in paper; ahand-builder in textiles; a binder in particleboard, medium-densityfiberboard, plywood, foundry and shell moldings, insulation materialsincluding glass fiber mats, friction materials, coated and bondedabrasives, etc.; a component in molding compounds; an adhesive for woodand laminates; a film-forming resin in coatings and printing inks; anadditive in fibers, e.g., rayon; an additive in rubber processing anagent in leather tanning; a textile size; a dry fixative for textiles;an impregnant for filters, e.g., automotive filters; and the like.

In order that the present invention may be more fully understood, thefollowing examples are given by way of illustration. No specific detailscontained therein should be construed as limitations on the presentinvention except insofar as they appear in the appended claims. Unlessotherwise specified, all parts and percentages are by weight.

EXAMPLE 1

290 Parts (2 moles) of a 40% aqueous solution of glyoxal was adjusted topH 6.5 with sodium bicarbonate. 176 Parts (2 moles) of ethylene urea wasadded and the temperature raised to 55±5° C. The mixture was stirred atthis temperature for two hours, maintaining the pH between 6.0 and 7.0.After two hours 200 parts (6.25 moles) of methanol was added and the pHadjusted to about 3.0 with concentrated sulfuric acid. The reaction washeld at reflux for three hours to effect methylation, the resin solutioncooled to 30° C., and the pH adjusted to about 7.0 with a 25% solutionof caustic soda.

The product was a clear viscous liquid, pale yellow, with negligibleodor. The reaction was essentially complete, as determined by IR and NMRanalyses. IR analysis indicated that methylation had occurred.

EXAMPLE 2

360 Parts (2.5 moles) of a 40% aqueous solution of glyoxal was added to905 parts (2.5 moles) of a 44% methanol solution of dimethyl methoxypropylene urea. The mixture was heated to 55±5° C. for two hours, the pHbeing maintained between 6.0 and 7.0. After cooling at 30° C. there wasobtained a 45%-solids, slightly viscous, water-white solution with noodor of formaldehyde. The reaction was essentially complete, asdetermined by IR and NMR analyses.

EXAMPLE 3

The procedure of Example 1 was repeated except that the glyoxal wasreacted with each of the following instead of ethylene urea: propyleneurea, uron, tetrahydro-5-(2-hydroxyethyl)-1,3,5-triazin-2-one, and4,5-dihydroxy-2-imidazolidinone. The results were comparable.

EXAMPLE 4

The procedure of Example 1 was repeated except that each of thefollowing alcohols was used instead of methanol: ethanol, n-propanol,and isopropanol. The results were comparable.

EXAMPLE 5

The resin product of Example 1 was used to treat 100% cotton fabric. Thetest results are tabulated below and compared with those of a sample ofthe same fabric treated with a conventional formaldehyde-containingagent. In each case the solution of resin and catalyst was applied tosamples of the fabric by padding with a wet pickup of about 60%, basedon the weight of the fabric. The treated fabrics were dried by heatingfor 3 minutes at 107° C., and the resin cured on the fabrics by heatingfor 90 seconds at 171° C.

Wrinkle Recovery was measured by AATCC Test Method 66-1978 "WrinkleRecovery of Fabrics: Recovery Angle Method".

Tensile was measured by ASTM Test Method D-1682-64 (Reapproved 1975)"Tensile-Grab-CRT Pendulum Type".

                  TABLE I                                                         ______________________________________                                                      (a)     (b)       (c)                                           ______________________________________                                         Reactant, parts                                                               A              15.0                                                           B                        15.0                                                Catalyst 531, parts                                                                           4.5       4.5                                                 Sulfanole® RWD, part                                                                      0.25      0.25                                                Tensile                                                                        warp           40        40         89                                        fill           16        15         37                                       Wrinkle Recovery                                                              initial         245       286       168                                       after 5 AHL     245       280       173                                       ______________________________________                                         A is the product of Example 1.                                                B is 1,3bishydroxymethyl-4,5-dihydroxy-2-imidazolidinone (45% aqueous         solution).                                                                    (c) is untreated 100% cotton fabric.                                          Catalyst 531 (Sun Chemical Corporation) is an activated magnesium chlorid     catalyst.                                                                     Sulfanole® RWD (Sun Chemical Corporation) is a nonionic wetting agent     AHL is average home launderings. home launderings.                       

From these data it can be seen that the fabric treated with the productof this invention (a) is comparable in tensile strength and wrinklerecovery to the fabric treated with a commercial formaldehyde-containingagent (b) and has the advantage of being free of formaldehyde.

EXAMPLE 6

The procedure of Example 5 was repeated with the resin products ofExamples 2, 3, and 4. The results were comparable.

EXAMPLE 7

An aqueous solution containing 15.0 parts of the resin product ofExample 1 and 4.0 parts of Catalyst 531 was applied to samples of 65/35polyester/cotton fabric by padding. The treated fabrics were dried; theresin cured on the fabrics by heating for 5 minutes at 150° C., 5minutes at 177° C., and 1 minute at 193° C.; and the fabric smoothnessdetermined by AATCC Test Method 124-1978 "Appearance of Durable PressFabrics after Repeated Home Launderings". The results are tabulatedbelow.

                  TABLE II                                                        ______________________________________                                        Fabric Smoothness (a)        (d)                                              ______________________________________                                        after    1 AHL                                                                         150° C.                                                                             3.7        3.2                                                   177° C.                                                                             3.6        3.1                                                   193° C.                                                                             3.4        3.0                                          after    5 AHL                                                                         150° C.                                                                             3.5        3.1                                                   177° C.                                                                             3.7        3.1                                                   193° C.                                                                             3.6        3.1                                          after    10 AHL                                                                        150° C.                                                                             3.4        3.2                                                   177° C.                                                                             3.8        3.2                                                   193° C.                                                                             3.8        3.2                                          ______________________________________                                         (d) is untreated 65/35 polyester/cotton fabric.                          

The whiteness of the fabric (a) was good, and the fabric showed nochlorine scorch either initially or after 5 launderings.

EXAMPLE 8

The following solutions were prepared, applied to 100% cotton, andtensile and wrinkle recovery measured as in Example 5:

                  TABLE III                                                       ______________________________________                                                      (a)     (e)       (c)                                           ______________________________________                                         Reactant, parts                                                               A              15.0                                                           C                        15.0                                                Catalyst 531, parts                                                                           4.5       4.5                                                 Sulfanole® RWD, part                                                                      0.25      0.25                                                Tensile                                                                        warp           40        41         89                                        fill           16        17         37                                       Wrinkle Recovery                                                              initial         245       199       168                                       after 5 AHL     245       187       173                                       ______________________________________                                         A is the product of Example 1.                                                C is the product of the reaction of stoichiometric amounts of glyoxal and     dimethyl urea (disclosed in U. S. Pat. No. 3,260,565).                        (c) is untreated 100% cotton fabric.                                     

From these data it can be seen that the fabric treated with the productof this invention (a) is comparable in tensile strength to the fabrictreated with the reactant disclosed in U.S. Pat. No. 3,260,565 (e) andconsiderably superior to it in wrinkle recovery.

EXAMPLE 9

The procedure of Example 5 was repeated with each of the followingfabrics instead of 100% cotton: 50/50 polyester/cotton, 65/35polyester/cotton, 50/50 polyester/rayon, and 65/35 polyester/rayon. Theresults were comparable.

EXAMPLE 10

A sample of 65/35 polyester/cotton fabric was impregnated with anaqueous solution containing 20 parts of the product of Example 1, 5parts of Catalyst KR (Sun Chemical Corporation's magnesium chloridecatalyst), and 0.25 part of Sulfanole RWD. The fabric was then dried at100° C. and stored at elevated temperature for several weeks. A creasewas then pressed into the fabric, and it was cured for 15 minutes at150° C. The fabric was washed and evaluated by AATCC Test Method88C-1975 "Appearance of Creases in Wash-and-Wear Items after HomeLaundering". It had an appearance rating of 5 as compared with a blankhaving a rating of 3.

EXAMPLE 11

To illustrate the superiority of an alkylated glyoxal/cyclic ureacondensate over a nonalkylated glyoxal/cyclic urea condensate, thefollowing experiments were carried out:

(1) 176 Parts of ethylene urea (2 moles) was reacted with 320 parts of40% glyoxal (2.2 moles) at a pH of 6 and a temperature of 50°-60° C. fortwo hours. The product was then reacted with 200 parts of methanol (6.25moles) at pH 3.0, and then adjusted to pH 6.0 and 45% solids. Thetemperature was lowered to, and held at, 48° C., and viscositymeasurements were taken at intervals with a Brookfield Viscometer.

(2) 176 Parts of ethylene urea (2 moles) was reacted with 320 parts of40% glyoxal (2.2 moles) at a pH of 6 and a temperature of 50°-60° C. fortwo hours. The product was adjusted with water to 45% solids. Thetemperature was lowered to, and held at, 48° C., and viscositymeasurements were taken at intervals with a Brookfield Viscometer.

                  TABLE IV                                                        ______________________________________                                        Viscosity, cps                                                                             (1)           (2)                                                ______________________________________                                        initial      52            26.5                                               after weeks - 1                                                                            65            gelled                                             2            107.5                                                            3            115                                                              4            127.5                                                            8            210                                                              9            232                                                              10           240                                                              ______________________________________                                    

From these data it can be seen that the nonalkylated product (2) wasunstable, gelling in one week, whereas the alkylated product (1)remained stable after 10 weeks at 48° C.

EXAMPLE 12

To illustrate the superiority of an alkylated glyoxal/cyclic ureacondensate over a nonalkylated glyoxal/cyclic urea condensate as atextile treating agent, the following experiments were carried out:

(1) Japanese publication No. 5 3044-567- Example 1

300 Grams of ethylene urea was charged into a 4-necked flask equippedwith a reflux condenser, a thermometer, and a stirrer and dissolved in450 grams of water. Then 1 kg. of 40% glyoxal (glyoxal:ethylene urearatio of 2:1) and 2 grams of concentrated hydrochloric acid were added.The mixture was reacted for three hours at 40° C. After cooling, the pHwas adjusted to 5.0 with sodium hydroxide solution. The slightly coloredtransparent product had a solids content of 40%.

(2) Japanese publication No. 5 3044-567- Example 2

300 Grams of ethylene urea was charged into a flask as in (1) anddissolved in 450 grams of water. 750 Grams of 40% glyoxal(glyoxal:ethylene urea ratio of 1.5:1) and 2 grams of concentratedhydrochloric acid were added. The mixture was reacted for three hours at40° C. After cooling, the pH was adjusted to 5.0 with sodium hydroxidesolution. The slightly colored transparent product had a solids contentof 40%.

15 Parts of each of these products and of the product of Example 1 waseach mixed with 3.75 parts of an activated magnesium chloride catalystand 0.25 part of Sulfanole RWD, and the solutions were applied bypadding to samples of fabric. The treated fabrics were dried for 3minutes at 107° C. and the resin cured on the fabrics by heating for 90seconds at 177° C.

The blue and whiteness indexes of each were measured by AATCC TestMethod 110-1975 and are tabulated as follows:

                  TABLE V                                                         ______________________________________                                                      (a)   (f)     (g)     (h)                                       ______________________________________                                        cotton                                                                        blue index      81.85   74.83   76.16 85.46                                   whiteness index 65.53   42.04   47.69 78.23                                   65/35 polyester/cotton                                                        blue index      78.99   70.07   72.51 82.35                                   whiteness index 57.63   29.51   37.74 67.62                                   ______________________________________                                         (a) is the product of Example 1 of this application.                          (f) is the product of Example 1 of Japanese publication No. 5 3044567.        (g) is the product of Example 2 of Japanese publication No. 5 3044567.        (h) is untreated fabric.                                                 

It is evident from these data that the product of this invention (a) issuperior to the products of the Japanese publication (f) and (g) in bothblue index and whiteness index. In addition, it was noted that the dryscorch on the fabrics treated with products (f) and (g) was extremelysevere.

What is claimed is:
 1. The alkylated product of the reaction ofapproximately stoichiometric amounts of glyoxal and one or more cyclicureas.
 2. The product of claim 1 wherein the ratio of glyoxal:cyclicurea is about 0.8-1.2:1.
 3. The product of the claim 1 wherein thecyclic urea has the following formula: ##STR2## wherein R₁, R₂, R₃, R₄,R₅, and R₆ may be the same or different and each may be H, OH, COOH, R,OR, or COOR wherein R is an alkyl or a substituted alkyl group having 1to 4 carbon atoms, and X may be C, O, or N; when X is O, R₃ and R₄ areeach zero; when X is N, R₃ or R₄ is zero.
 4. A water-soluble resinousproduct prepared by alkylating the product of the condensation ofglyoxal and at least one cyclic urea, the ratio of glyoxal:cyclic ureabeing about 0.8-1.2:1.
 5. The resinous product prepared by condensingglyoxal with at least one alkylated cyclic urea of claim 3.